A Nine-Dimensional Calculation of the Vibrational OH Stretching and HOH Bending Spectrum of the Water Trimer

Salmi, Teemu; Sälli, Elina; Halonen, Lauri

doi:10.1021/jp3017584

Cited by 14 publications

(16 citation statements)

References 47 publications

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“…The remaining three modes were collective, slow motions with the frequency less than 100 cm −1 (also shown in Figure S1). The effect of these modes on the resulting IR spectrum is unknown; yet we note that the IR spectrum of neutral water clusters has been calculated reasonably well with similar settings, for example, for a trimer 53 and a hexamer. 54 Note also that the present model includes O•••O (or water•••water) stretching modes that modulate the hydrogen bond distance and are known to affect high frequency motions significantly.…”

Section: Methodsmentioning

confidence: 71%

Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Yagi

Thomsen

2017

J. Phys. Chem. A

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The infrared spectrum of H(HO) recently observed in a wide spectral range has shown a series of bands in a range of 1700-2500 cm, which can not be understood by the standard harmonic normal mode analysis. Here, we theoretically investigate the origin of these bands with a focus on (1) the possibility of coexistence of multiple isomers in the Eigen [HO(HO)] and Zundel [HO(HO)] forms and (2) the effect of anharmonic coupling that gives rise to nonzero intensities for overtones and combination bands. Anharmonic vibrational calculations are carried out for the Eigen and Zundel clusters by the second-order vibrational quasi-degenerate perturbation theory (VQDPT2) based on optimized coordinates. The anharmonic potential energy surface and the dipole moment surfaces are generated by a multiresolution approach combining one-dimensional (1D) grid potential functions derived from CCSD(T)-F12, 2D and 3D grid potential functions derived from B3LYP for important coupling terms, and a quartic force field derived from B3LYP for less important terms. The spectrum calculated for the Eigen cluster is in excellent agreement with the experiment, assigning the bands in the range of 1700-2500 cm to overtones and combination bands of a HO moiety in line with recent reports [ J. Phys. Chem. A 2015 , 119 , 9425 ; Science 2016 , 354 , 1131 ]. On the other hand, characteristic OH stretching bands of the Zundel cluster is found to be absent in the experimental spectrum. We therefore conclude that the experimental spectrum originates solely from the Eigen cluster. Nonetheless, the present calculation for the Eigen cluster poorly reproduces a band observed at 1765 cm. A possible nature of this band is discussed.

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Section: Methodsmentioning

confidence: 71%

Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Yagi

Thomsen

2017

J. Phys. Chem. A

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“…The strategy was followed by a number of works on the water dimer, 53, 54 trimer, [54][55][56] and the clusters up to pentamer. 57 Recently, Wang and Bowman 58 have introduced a further approximation, which neglects the inter-water coupling in the potential using a set of coordinates localized to each water molecule.…”

Section: Overviewmentioning

confidence: 99%

Optimized coordinates in vibrational coupled cluster calculations

Thomsen

Yagi

Christiansen

2014

The Journal of Chemical Physics

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Articles you may be interested inOrbitally invariant internally contracted multireference unitary coupled cluster theory and its perturbative approximation: Theory and test calculations of second order approximation J. Chem. Phys. 137, 014108 (2012); 10.1063/1.4731634 Accurate calculation of vibrational frequencies using explicitly correlated coupled-cluster theory Accurate calculation of anharmonic vibrational frequencies of medium sized molecules using local coupled cluster methods J. Chem. Phys. 126, 134108 (2007); 10.1063/1.2718951 MRCI calculations on the helium dimer employing an interaction optimized basis setThe use of variationally optimized coordinates, which minimize the vibrational self-consistent field (VSCF) ground state energy with respect to orthogonal transformations of the coordinates, has recently been shown to improve the convergence of vibrational configuration interaction (VCI) towards the exact full VCI [K. Yagi, M. Keçeli, and S. Hirata, J. Chem. Phys. 137, 204118 (2012)]. The present paper proposes an incorporation of optimized coordinates into the vibrational coupled cluster (VCC), which has in the past been shown to outperform VCI in approximate calculations where similar restricted state spaces are employed in VCI and VCC. An embarrassingly parallel algorithm for variational optimization of coordinates for VSCF is implemented and the resulting coordinates and potentials are introduced into a VCC program. The performance of VCC in optimized coordinates (denoted oc-VCC) is examined through pilot applications to water, formaldehyde, and a series of water clusters (dimer, trimer, and hexamer) by comparing the calculated vibrational energy levels with those of the conventional VCC in normal coordinates and VCI in optimized coordinates. For water clusters, in particular, oc-VCC is found to gain orders of magnitude improvement in the accuracy, exemplifying that the combination of optimized coordinates localized to each monomer with the size-extensive VCC wave function provides a supreme description of systems consisting of weakly interacting sub-systems.

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“…The nonadditivity is a many-body effect, studied extensively for developing improved potential energy functions (PEFs) for water . Indeed, such PEFs , can be substantially more accurate than the customary semiempirical force fields, as exemplified by the MB-pol water potential from the Paesani group. − …”

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Intramolecular Vibrational Bands in Small Water Clusters

Samala

Agmon

2019

J. Phys. Chem. B

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Cyclic water clusters are pivotal for understanding atmospheric reactions as well as liquid water, yet the temperature (T) dependence of their dynamics and spectroscopy is poorly studied. The development of highly accurate water potentials, such as MB-pol, partly rectifies this. It remains to account for the quantum nuclear effects (NQE), because quantum nuclear dynamics become increasingly inaccurate at low temperatures. From a practical point of view, we find that NQE can be accounted for simply by subtracting a constant from the frequencies obtained from the velocity autocorrelation functions (VACF) of classical nuclear dynamics, resulting in unprecedented agreement with experiment, mostly within 5 cm–1. We have performed classical simulations of (H2O) n clusters (n = 2–5) from 20 K and up to their melting temperature, calculating both all-atom and partial VACF, thus generating the temperature dependence of the vibrational frequencies (IR and Raman bands). Focusing on the hydrogen-bonded (HBed) OH stretch and HOH bend, we find opposing T dependencies. The HBed OH modes blue shift linearly with T, attributed to ring expansion rather than any specific conformational change. The lowest-frequency Raman concerted mode is predicted to show the largest such shift. In contrast, the HOH bend undergoes a red-shift, with the highest frequency concerted band undergoing the largest red-shift. These results can be explained by a coupled-oscillator model for n hydrogen atoms on a ring, constrained to move either tangentially (stretch) or perpendicularly (bend) to the ring. With increasing temperature and weakening of HBs, the intrinsic force constant increases (stretch) or remains constant (bend), while the nearest-neighbor coupling constant decreases, and this results in the interesting behavior revealed herein. T-dependent Raman studies are required for testing some of these predictions.

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A Nine-Dimensional Calculation of the Vibrational OH Stretching and HOH Bending Spectrum of the Water Trimer

Cited by 14 publications

References 47 publications

Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Optimized coordinates in vibrational coupled cluster calculations

Temperature Dependence of Intramolecular Vibrational Bands in Small Water Clusters

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A Nine-Dimensional Calculation of the Vibrational OH Stretching and HOH Bending Spectrum of the Water Trimer

Cited by 14 publications

References 47 publications

Infrared Spectra of Protonated Water Clusters, H+(H2O)4, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Infrared Spectra of Protonated Water Clusters, H+(H2O)4, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Optimized coordinates in vibrational coupled cluster calculations

Temperature Dependence of Intramolecular Vibrational Bands in Small Water Clusters

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Product

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Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory

Infrared Spectra of Protonated Water Clusters, H⁺(H₂O)₄, in Eigen and Zundel Forms Studied by Vibrational Quasi-Degenerate Perturbation Theory